Note: Descriptions are shown in the official language in which they were submitted.
CA 02987581 2017-11-28
WO 2017/011065 PCMJS2016/031704
1
THIODIESTER PLASTICIZERS
HELD OF THE INVENTION
[001] The present invention relates to dialkyl thiodiester plasticizers,
their blend plasticizer
compositions and use for plasticizing halogen-containing polymers, such as
polyvinyl chloride or
rubber. More particularly, the present invention relates to plasticizer
compositions for plasticizing
halogenated polymers or rubber comprising: (i) a dialkyl thiodiester selected
from dialkyl 3,3' -
thiodipropionate, dialkyl 2,2'-thiodiacetate or mixtures thereof; and (ii)
epoxidized material
selected from epoxidized oils, epoxidized fatty acid mono-esters, reaction
mixtures prepared via
trans-esterifying epoxidized oil with alcohols or esters, or mixtures thereof.
BACKGROUND OF THE INVENTION
[002] Polyvinyl chloride ("PVC") is in wide commercial use because of its
superior
performance and properties. Modern consumers utilize PVC-containing products
throughout their
daily activities, since it is a primary ingredient in profiles, sidings,
floorings, wall-coverings,
films/sheets, fabrics, pipes, fittings and coatings. Various additives, such
as plasticizers, are
commonly included when formulating flexible compositions containing PVC.
Plasticizers are
necessary when the end-use application of the PVC requires flexibility, such
as in the manufacture
of films, sheets and coatings. However, some plasticizers can migrate out of
the plasticized
product, and can even be lost into the environment through evaporation or
extraction by liquids
that come into contact with the plasticized material. The loss of plasticizer
from the plasticized
article is undesirable, both because it adversely affects the properties of
the plasticized product,
and because it represents a loss of chemicals into the environment. Efforts
have been ongoing to
develop plasticizers having improved properties from the standpoint of
efficiency, volatility and
extraction.
[003] U.S. Patent No. 2,356,586 discloses the use of esters of thio
diglycol, such as
S(CH2CH2OH)2 or S(CH2CH/CH7OH)2, with mono-basic aliphatic carboxylic acid
comprising
from seven to nine atoms in the molecule as plasticizers for PVC and the
corresponding PVC
compounds.
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
2
[004] U.S. Patent No. 2,530,882 discloses plasticizers for vinyl resins,
such as PVC. The
plasticizer is an ester of a sulfur-containing polycarboxylic acid. The acid
contains from 2 to 4
sulfur atoms.
[005] U.S. Patent No. 2,668,847 discloses the preparation and use of tetra-
alkylthioesters, such
as tetrabutyl thio di-succinate, prepared by reacting a di-ester of an
unsaturated dicarboxylic acid,
or a tri-ester of an unsaturated olefinic tricarboxylic acid with hydrogen
sulfide.
[006] U.S. Patent Nos, 4,340,514 and 6,362,264 disclose the use of 3,3'-
thiodipropionates,
such as dilauryl 3,3'-thiodipropionate (DLTDP) and distearyl 3,3'-
thiodipropionate (DSTDP), as
components of heat stabilizers for PVC. The concentration of the
thiodipropionates in PVC did
not exceed 1%.
[007] U.S. Patent No. 5,286,788 discloses the use of 3,3'-
thiodipropionates, such as dimethyl
3,3'-thiodipropionate and di-tridecyl 3,3' -thiodipropionate, as additives
that reduce the heat of
curing of unsaturated polyester and vinyl ester resins. The additives were
used at 0.5%.
[008] U.S. Patent No. 5,665,504 discloses using thiodipropionates as
components of light
fastness inducing agents.
[009] The International Journal of Toxicology, 29 (supplement 3), p. 137S-
150S (2010)
discloses that dialkyl 3,3'-thiodipropionate esters, such as dilauryl 3,3' -
thiodipropionate and
ditridecyl 3,3' -thiodipropionate, are not sensitizers and find applications
in cosmetics. Their
concentration there does not exceed 4%.
[0010] The Plastics Additives Handbook, 4th edition, 1996, p. 46. discloses
that dialkyl 3,3'-
thiodipropionates, such as DLTDP and DSTDP, are known to be used as
stabilizers for polyolefins,
such as polyethylene, polypropylene and polystyrene, to improve their weather
and heat resistance.
DLTDP is also used as an antioxidant for fats, oils, PVC. ABS, acrylic resins
and other plastics
SUMMARY OF THE INVENTION
[0011] The subject matter of the present disclosure relates to plasticizer
compositions
containing a dialkyl thiodiester. In one embodiment, the present disclosure
provides a plasticizer
composition for plasticizing halogenated polymers or rubber comprising: (i) a
dialkyl thiodiester
selected from dialkyl 3,3'-thiodipropionate, dialkyl 2,2'-thiodiacetate or
mixtures thereof, where
the alkyl groups are the same or different and are selected from C i-C is
linear, branched, cyclic or
aromatic groups; and (ii) epoxidized material selected from epoxidized oils,
epoxidized fatty acid
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
3
mono-esters, reaction mixtures prepared via trans-esterifying epoxidized oil
with alcohols or esters
or mixtures thereof. The plasticizer composition may also contain mono-
glycerides and/or di-
glycerides.
[0012] In another embodiment, the present disclosure provides a plasticizer
composition for
plasticizing halogenated polymers or rubber comprising: (i) a dialkyl
thiodiester selected from
dialkyl 3,3' -thiodipropionate, dialkyl 2,2' -thiodiacetate or mixtures
thereof, where the alkyl
groups are the same or different and are selected from Cl-Ci 8 linear,
branched, cyclic or aromatic
groups; and (iii) at least one conventional plasticizer selected from the
group consisting of
phthalates, substantially fully esterified mono-, di- and tribasic acids,
adipates, azelates, succinates,
glutarates, glycol esters, sucrose esters, levulinic ketal esters, citrates,
phosphates, alkyl phenol
sulfonates, pyrrolidones and mixtures thereof.
[0013] In still another embodiment, the present disclosure provides a
process comprising
adding an effective amount of a plasticizer composition to a halogenated
polymer or rubber, the
plasticizer composition comprising a dialkyl thiodiester selected from dialkyl
3,3' -
thiodipropionate, dialkyl 2,2' -thiodiacetate or mixtures thereof, where the
alkyl groups are the
same or different and are selected from C1-C18 linear, branched, cyclic or
aromatic groups, thereby
forming a plasticized product.
[0014] In another embodiment, the present disclosure provides a PVC article
comprising a
plasticizer composition, the plasticizer composition comprising a dialkyl
thiodiester material
selected from dialkyl 3,3' -thiodipropionate, dialkyl 2,2' -thiodiacetate or
mixtures thereof, where
the alkyl groups are the same or different and are selected from Cl-C 8
linear, branched, cyclic or
aromatic groups.
100151 In still another embodiment, the present disclosure provides a
plasticized polyvinyl
chloride composition prepared by a process comprising the steps of: (a)
providing a dialkyl
thiodiester plasticizer selected from dialkyl 3,3'-thiodipropionate, dialkyl
2,2'-thiodiacetate or
mixtures thereof, where the alkyl groups are the same or different and are
selected from Cl-C18
linear, branched, cyclic or aromatic groups, and optionally blending it with
an epoxidized oil, an
epoxidized monoester of fatty acid, reaction mixtures prepared via trans-
esterifying epoxidized oil
with alcohols or esters, or mixtures thereof, and (b) adding the plasticizer
to polyvinyl chloride in
an amount of from 1 to 200 parts per 100 parts of polyvinyl chloride, at a
temperature in the range
of from 10-300 C.
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
4
[0016] In still another embodiment, the present disclosure provides a process
for producing a PVC
dry blend composition, the process comprising compounding polyvinyl chloride,
a plasticizer, and
a filler at a temperature between 25 and 70 C for a time effective to form a
dry mixture having a
bulk density greater than 0.5 g/cc, wherein the plasticizer comprises: (i) a
dialkyl thiodiester
selected from dialkyl 3,3'-thiodipropionate, dialkyl 2,2'-thiodiacetate or
mixtures thereof, where
the alkyl groups are the same or different and are selected from Ci-C I 8
linear, branched, cyclic or
aromatic groups; and (ii) epoxidized material selected from epoxidized oils,
epoxidized fatty acid
mono-esters, reaction mixtures prepared via trans-esterifying epoxidized oil
with alcohols or
esters, or mixtures thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The subject matter of the present disclosure provides a plasticizer
composition for
plasticizing halogenated polymers or rubber comprising: (i) dialkyl
thiodiester selected from
dialkyl 3.3' -thiodipropionate, dialkyl 2,2'-thiodiacetate or mixtures
thereof, where the alkyl
groups are the same or different and are selected from Ci-Cis linear,
branched, cyclic or aromatic
groups; and (ii) epoxidized material selected from epoxidized oils, epoxidized
fatty acid mono-
esters, reaction mixtures prepared via trans-esterifying epoxidized oil with
alcohols or esters, or
mixtures thereof. It has surprisingly been found that such plasticizer
compositions are effective
plasticizers for chlorine-containing containing polymers, such as polyvinyl
chloride. PVC-based
co-polymers, terpolymers, and grafted polymers and rubber. The plasticizer
compositions provide
low volatility and cold temperature flexibility to plasticized halogenated
polymers.
Dialkyl thiodiester material
[0018] The dialkyl thiodiester in the plasticizers of the current subject
matter is selected from
dialkyl 3,3' -thiodipropionate, di alkyl 2,2' -thiodi acetate or mixtures
thereof, where the alkyl
groups are the same or different, and are selected from Cl-C18 linear,
branched, cyclic or aromatic
groups. Preferably, the alkyl groups are independently selected from the group
consisting of iso-
octyl, 2-ethylhexyl, nonyl, decyl, and dodecyl. Even more preferably, the
alkyl groups are 2-
ethylhexyl. Preferably, the dialkyl thiodiester is di(2-ethylhexyl) 3,3' -
thiodipropionate.
[0019] The dialkyl thiodiester can be obtained via conventional methods,
including a) reacting
an alkyl acrylate with H2S, b) esterifying 3,3'-thiodipropionic acid or 2,2' -
theiodiacetic acid with
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
an alcohol, c) reacting thiodipropionitrile or thiodiacetonitrile with an
alcohol, and d) trans-
esterifying dimethyl 3,3' -thiodipropionate or dimethyl 2,2'-thiodiacetate
with an alcohol, where
the alkyl group of the ester is Ci-Cis and of the alcohol is of C2-C18.
Preferably, the alcohol is 2-
ethylhexanol.
Epoxidized Material
[0020] The epoxidized material in the plasticizer of the present disclosure
is selected from
epoxidized oils, epoxidized fatty acid monoesters, reaction mixtures prepared
via trans-esterifying
epoxidized oil with alcohols (such as methanol or ethanol) or esters (such as
ethyl acetate) or
mixtures thereof.
Epoxidized Fatty Acid Mono Esters
[0021] When the epoxidized material contains an epoxidized fatty acid mono-
ester, the
epoxidized fatty acid mono-ester comprises a fatty acid derived from natural
oil or animal fat.
When the epoxidized fatty acid mono-ester comprises a fatty acid derived from
a natural oil, the
natural oil is selected from the group consisting of soybean oil, palm oil,
olive oil, tall oil, cotton
seed oil, linseed oil. safflower oil, sunflower oil, canola oil, rapeseed oil,
jatropha oil, algae oil,
corn oil. tung oil, and mixtures thereof. More preferably, the natural oil is
selected from soybean
oil, linseed oil or tall oil.
[0022] Preferably, the fatty acid of the fatty acid mono-ester is selected
from the group
consisting of oleic acid, linoleic acid. linolenic acid, dehydrated ricinoleic
acid, and mixtures
thereof. The fatty acid is preferably substantially fully esterified with a
monohydric alcohol. For
the purposes of this specification, the term, "substantially fully esterified"
means at least 50% of
the acid is converted to the ester.
[0023] The monohydric alcohol is typically selected from methanol, ethanol,
n-propanol,
isopropanol, iso-butanol, pentanol, hexanol, cyclohexanol, octanol, 2-
ethylhexanol, nonanol,
decanol, dodecanol, neododecanol, and neodecanol. Preferably, the monohydric
alcohol has at
least three carbon atoms. More preferably, the monohydric alcohol has at least
eight, ten, twelve,
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
6
or eighteen carbon atoms. Most preferably, the monohydric alcohol has at least
eight carbon
atoms.
[0024] The fatty acid also preferably comprises unsaturation, where the
unsaturation is
preferably substantially fully epoxidized. For the purposes of this
specification, the term
"substantially fully epoxidized" means at least 50% of double bonds are
converted to epoxy
groups. Suitable examples of epoxidized mono-esters include epoxidized 2-
ethylhexyl tallate,
epoxidized 2-ethyhexyl soyate, epoxidized octyl tallate, epoxidized octyl
soyate, epoxidized
methyl soyate, epoxidized octyl oleate or mixtures thereof. More preferably,
the epoxidized mono-
ester is selected from epoxidized 2-ethyhexyl tallate or epoxidized 2-
ethylhexyl soyate. The
epoxidized fatty acid monoesters may also contain mono-glycerides and/or di-
glycerides, such as
epoxidized methyl soybean oil diglyceride, epoxidized 2-ethylhexyl soybean oil
diglyceride,
epxidized dimethyl glyceride and epxodizied bis(2-ethylhexyl) soybean oil
glyceride.
Trans-esterification of epoxidized oil
[0025] The epoxidized material can also be a reaction mixture prepared via
trans-esterifying
epoxidized oil with alcohols, esters or mixtures thereof. The epoxidized oils
can be based on
vegetable and other natural oils. Suitable vegetable and natural oils include,
for example, canola
oil, corn oil, linseed oil, rapeseed oil, safflower oil, soybean oil,
sunflower oil, jatropha oil, algae
oil, castor oil, tung oil, tall oil. fish oil and mixtures thereof. Suitable
alcohols include methanol,
ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 1-hexanol, 1-octanol.
2-ethylhexyl alcohol,
1-decanol, cyclohexanol, benzyl alcohol, and allyl alcohol. Suitable esters
include ethyl acetate.
Epoxidized Oils
[0026] When the epoxidized material contains an epoxidized oil, the epoxidized
oils are derived
from plant oils, fish oils or animal fats. Suitable natural oils include
vegetable oils and other plant
oils, which may also contain triglyceride esters of fatty acids such as
soybean oil, palm oil, olive
oil, tall oil, castor oil, cotton seed oil, linseed oil, safflower oil,
sunflower oil, canola oil, rapeseed
oil, jatropha oil, algae oil, corn oil, tung oil, and mixtures of any two or
more thereof. Preferred
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
7
natural oils include soybean oil, linseed oil, and tall oil. Suitable animal
fats include beef/mutton,
pork, dairy, poultry fat, to name a few. Of these, suet, dripping, tallow,
lard, bacon, fatback, butter,
poultry fat, schmaltz, blubber, and the like, are preferred.
[0027] Most preferably, the epoxidized oils are epoxidized soybean oil or
epoxidized linseed
oil.
[0028] The plasticizer composition of the present disclosure contains
dialkyl thiodiester and
epoxidized material, where the dialkyl thiodiester is present in an amount
from 20 to 99 wt% and
the epoxidized material is present in an amount from l to 80 wt%, based on the
total weight of the
dialkyl thiodiester and the epoxidized material. Preferably, the dialkyl
thiodiester is present in an
amount from 25 to 95 wt% and the epoxidized material is present in an amount
from 5 to 75 wt%.
The plasticizer compositions preferably include blends of di(2-ethylhexyl)
3,3'-thiodipropionate
with epoxidized soybean oil, epoxidized 2-ethylhexyl soyate, epoxidized 2-
ethylhexyl tallate,
epoxidized methyl soyate, reaction mixtures prepared via trans-esterifying
epoxidized soybean oil
with alcohols (such as methanol or ethanol) or esters (such as ethyl acetate),
and mixtures thereof.
In certain embodiments, the blends may be stable, homogeneous, liquid
mixtures.
[0029] The plasticizer compositions of the present subject matter
advantageously provide: a)
reduced plasticizer content due to high plasticizing efficiency in the
plasticized articles, b) reduced
volatility of the plasticized halogen-containing polymers or rubber, c)
increased low temperature
flexibility, d) reduced plasticizer extraction from the plasticized halogen-
containing polymers or
rubber, c) increased volume resistivity of the plasticized compounds, f)
enhanced heat stability and
g) acceptable UV stability.
[0030] In another embodiment, the present subject matter includes a
plasticizer composition for
plasticizing halogenated polymers or rubber comprising: (i) a dialkyl
thiodiester selected from
dialkyl 3.3' -thiodipropionate, dialkyl 2,2'-thiodiacetate or mixtures
thereof, where the alkyl
groups are the same or different and are selected from Ci-Cis linear,
branched, cyclic or aromatic
groups; and (iii) at least one conventional plasticizer. Exemplary
conventional plasticizers are
branched and linear phthalates, hydrogenated phthalates, aliphatic esters of
dicarboxylic acids,
8
polymeric esters of dicarboxylic acids, citrates, sucrose esters, levulinic
ketal esters, phosphates,
alkyl phenol sulfonates, pyrrolidones, trimellitates, esters of benzoic acid
and the like. An
overview of conventional plasticizers is found at PLASTICS ADDITIVES HANDBOOK,
4th
edition, ed. Gachter/Muller, Hansa Gardner Publishers, Munich, 1993, pg. 327-
422. Preferably,
the conventional plasticizers are selected from the group consisting of
phthalates, substantially
fully esterified mono-, di- and tribasic acids, adipates, azelates,
succinates, glutarates, glycol esters,
sucrose esters, levulinic ketal esters, citrates, phosphates, alkyl phenol
sulfonates, pyrrolidones and
mixtures thereof. The composition can optionally also contain (ii) epoxidized
material selected
from epoxidized oils, epoxidized fatty acid mono-esters, reaction mixtures
prepared via trans-
esterifying epoxidized oil with alcohols or esters, or mixtures thereof.
[0031] The plasticizer composition of the present subject matter can be
prepared by blending
in any of the known blending processes, methods and techniques, for example,
admixing and
mixing can be used to prepare the liquid blends for the purpose of attaining
homogeneity. In
some embodiments, the components are combined in an admixture, blended, and
maintained
with or without agitation for a predetermined amount of time at ambient
temperature. In one
embodiment, the predetermined amount of time is in the range of 1 to 24 hours.
Preferably, the
amount of time is from 1 to 10 hours, more preferably from one to four hours.
Preferably, the
components of the composition are combined at a temperature in the range of
from 10-100 C,
more preferably at a range of from 10-80 C, even more preferred from 20-60 C.
[0032] In another embodiment, the subject matter of the present disclosure
provides a process
comprising adding an effective amount of a plasticizer composition to a
halogenated polymer or
rubber, the plasticizer composition comprising a dialkyl thiodiester selected
from dialkyl 3,3' -
thiodipropionate, dialkyl 2,2'-thiodiacetate or mixtures thereof, where the
alkyl groups are the
same or different and are selected from C1-C18 linear, branched, cyclic or
aromatic groups, thereby
forming a plasticized compound. Preferably, the plasticizer composition
further comprises
epoxidized material selected from epoxidized oils, epoxidized fatty acid mono-
esters, reaction
mixtures prepared via trans-esterifying epoxidized soybean oil with alcohols
or esters, or mixtures
thereof.
Date Recue/Date Received 2020-10-05
9
[0033] The plasticized halogenated polymer or rubber compositions possess a
reduced volatility
and/or extraction when compared to an otherwise identical plasticized
halogenated polymers,
except for the presence of the plasticizer compositions of the present
disclosure. The plasticized
halogenated polymer preferably has a volatility of less than 5%, more
preferably, less than 3%, if
loaded with the above plasticizer at 40 phr, compounded into a 0.5 mm
plasticized PVC sheet and
measured at 100 C over a 168 hour period. The plasticized halogenated polymer
preferably has a
Shore A Hardness of less than 100, more preferably, less than 95, if loaded at
40 phr and
compounded into a 0.5 mm plasticized PVC sheet. Preferably, the plasticized
halogenated
polymer has a volume resistivity greater than E+12 Ohm=meter if the
plasticizer composition is
loaded at 40 phr into a PVC compound. The plasticized halogenated polymer
preferably has a
decomposition time greater than 60 minutes, if the plasticizer composition is
loaded at 40 phr and
compounded into a 0.5 mm plasticized PVC sheet.
[0034] The plasticizer compositions of the invention are useful, in
particular in the form of
flexible compounds, for articles such as wire sheathing, cable insulation and
jacketing, decoration
sheeting, roofing membranes, agricultural sheeting, hoses, tubing, sealing
profiles, floor coverings,
wall-coverings, artificial leather, films, injection moldings, office films,
films for air halls, textile
coatings, and coil coatings.
Additives
[0035] The plasticizer compositions of the present disclosure can also include
one or more
additives to enhance or modify chemical or physical properties, such as heat
stability, lubricity,
color, or viscosity. Exemplary additives include, but are not limited to, heat
stabilizers, lubricants,
viscosity control agents, UV absorbers, antioxidants, antistatic agents,
antimicrobials and
antifungal compounds, among other compounds conventionally used in flexible
PVC
formulations. An overview of these can be found in Plastics Additives
Handbook, 4th edition,
editors: R. Gachter and H. Muller, associate editor: P. P. Klemchuk; Hanser
Publishers, Munich,
(1993) and Plastics Additives and Modifiers Handbook, ed. J. Edenbaum; Van
Nostrand Reinhold,
(1992). Typical additives are summarized below.
I. Polyols and Other Organic Components
Date Recue/Date Received 2020-10-05
10
[0036] Suitable compounds of this type include sorbitol, triethanolamine,
polyethylene glycols,
I3-diketones, such as stearoyl-benzoylmethane, and uracils. The polyols are
used in amounts from
0.01 to 20 parts by weight, preferably from 0.1 to 10 parts by weight, and
more preferably from
0.1 to 5 parts by weight, based on 100 parts by weight of PVC.
II. Hydrotalcite Co-Stabilizers
[0037] The chemical composition of these compounds is known to one of ordinary
skill in the
art as disclosed in DE 3 843 581, U.S. Pat. No. 4,000,100, EP 0 062 813 and WO
93/20135.
[0038] Compounds from the hydrotalcite series may be described by the
following general
formula:
M2+i_xM3+x(OH)2(Ab-)xm - c/H20,
where
M2+=one or more of the metals selected from the group consisting of Mg, Ca,
Sr, Zn and
Sn,
M3+=A1 or B,
Ab is an anion of valency b,
b is a number from 1-2,
0<x<0.5, and
d is a number from 0-20.
[0039] Preferably, Ab is selected from OH-, C104-, HCO3, CH3C00-, C6H5C00-,
C032-,
(CHOHC00)22-, (CH2C00)22-,-CH3CHOHC00-, HP03- or HP042-. Examples of
hydrotalcites
include A1203-6Mg0-0O2-12H20, Mg4-5Al2(OH)13-0O3-3.5H20, 4Mg0-A1203CO2-9H20,
4Mg0A1203-0O26H20, ZnO -3Mg0 - Al2O3- CO2-8-9H20 and ZnO3Mg0A1203CO2-5-6H20.
III. Metal Soap Stabilizers
[0040] Metal soaps are primarily metal carboxylates, preferably of
relatively long-chain
carboxylic acids. Well-known examples of these are stearates, oleates,
palmitates, ricinolates,
hydroxystearates, dihydroxy-stearates and laurates.
[0041] Exemplary metals include alkali, alkaline earth and rare earth
metals. Preferably, the
metals are selected from Na, K, Mg, Ca, Sr, Ba, Pb, Zn, Al, La, or Ce. Use is
frequently made of
Date Recue/Date Received 2020-10-05
11
so-called synergistic mixtures, such as barium/zinc stabilizers,
magnesium/zinc stabilizers,
calcium/zinc stabilizers or calcium/magnesium/zinc stabilizers. The metal
soaps may be used
either alone or in mixtures. An overview of common metal soaps is found in
Ullmann's
Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A16 (1985), pp. 361 et
seq.
[0042] The metal soaps or mixtures thereof may be used in amounts of, for
example, 0.001 to
parts by weight, preferably, 0.01 to 8 parts by weight, more preferably 0.05
to 5 parts by weight,
based on 100 parts by weight of PVC.
IV. Alkali Metal and Alkaline Earth Metal Compounds
[0043] For the purposes of the present disclosure, examples of these
materials include the
carboxylates of the acids described above, but also the corresponding oxides,
hydroxides or
carbonates. Mixtures of these with organic acids are also possible. Examples
include NaOH,
KOH, CaO, Ca(OH)2, MgO, Mg(OH)2, BaO, Ba(OH)2, Sr(OH)2, Al(OH)3, CaCO3, MgCO3
and
the basic carbonates, as well as selected salts of Na and of K, including
perchlorates. In the case
of alkaline earth carboxylates and Zn carboxylates, it is also possible to use
adducts of these as so-
called "overbased" compounds.
V. Organotin Stabilizers
[0044] Examples of suitable compounds of this type include both mono- and
dimethyl, butyl
and octyltin mercaptides, maleates and the like.
VI. Phosphites (Triesters of Phosphorous Acid)
[0045] Organic phosphites are known co-stabilizers for chlorine-containing
polymers.
Examples of these are triphenyl phosphite, diphenyl isodecyl phosphite,
ethylhexyl diphenyl
phosphite, phenyl diisodecyl phosphite, trilauryl phosphite, triisononyl
phosphite, triisodecyl
phosphite, epoxy grade triphenyl phosphite, diphenyl phosphite, and
tris(nonylphenyl) phosphite.
Advantageous use may also be made of phosphites of various di- or polyols.
[0046] Preferably, the organic phosphites are used in amounts from 0.01 to
10 parts by weight,
more preferably from 0.05 to 5, and most preferably from 0.1 to 3 parts by
weight, based on 100
parts by weight of PVC.
Date Recue/Date Received 2020-10-05
12
VII. Lubricants
[0047] Examples of suitable lubricants include fatty acids, fatty alcohols,
montan wax, fatty
acid esters, PE waxes, amide waxes, chloroparaffins, glycerol esters, alkaline
earth metal soaps,
fatty ketones, and also the lubricants listed in EP0259783. Preferably, the
lubricants are selected
from stearic acid, stearic esters or calcium stearate.
VIII. Fillers
[0048] Suitable fillers include calcium carbonate, dolomite, wollastonite,
magnesium oxide,
magnesium hydroxide, silicates, china clay, talc, glass fibers, glass beads,
wood flour, mica, metal
oxides or metal hydroxides, carbon black, graphite, rock flour, heavy spar,
glass fibers, talc, kaolin
and chalk may be used in accordance with some embodiments of the present
invention, as in the
HANDBOOK OF PVC FORMULATING, E. J. Wickson, John Wiley & Sons, Inc., 1993, pp.
393-
449; see also TASCHENBUCH der Kunststoffadditive [Plastics Additives
Handbook], R. Gachter
& H. Muller, Carl Hanser, 1990, pp. 549-615).
[0049] The fillers are preferably used in amounts of 1 to 20 parts by
weight, more preferably,
1 to 10 parts by weight, and even more preferably from 1 to 5 parts by weight,
based on 100 parts
by weight of PVC.
IX. Pigments
[0050] Suitable pigments are known to those of ordinary skill in the art,
and include inorganic
pigments such as TiO2, pigments based on zirconium oxide, BaSO4, and zinc
oxide (zinc white).
Mixtures of various pigments may also be used, e.g., as shown in the "Handbook
of PVC
Formulating", E. J. Wickson, John Wiley & Sons, New York, 1993.
Date Recue/Date Received 2020-10-05
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
13
X. Antioxidants
[0051]
Exemplary embodiments include alkylated monophenols, e.g., 2,6-di-tert-buty1-4-
methylphenol, alkylthiomethylphenols, e.g., 2,4-dioctylthiomethy1-6-tert-
butylphenol, alkylated
hydroquinones, e.g., 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated
thiodiphenyl ethers, e.g.,
2,2'-thiobis(6-tert-butyl-4-methylphenol), alkylidenebisphenols, e.g., 2,2'-
methylene-bis(6-tert-
buty1-4-methylphenol), benzyl compounds, e.g., 3.5,3'.5'-tetratert-buty1-4,4'-
dihydroxydibenzyl
ether, hydroxybenzylated malonates, e.g., dioctadecyl 2,2-bis(3,5-di-tert-
buty1-2-
hydroxybenzyl)malonate, hydroxybenzyl
aromatics, e.g., 1,3,5 -tri s (3 ,5-di-tert-buty1-4-
hydroxyben zy1)-2,4,6-tri methylben zene, triazine compounds. e.g., 2,4-
bisoctylmercapto-6-(3,5-
di-tert-buty1-4-hydroxyanilino)-1,3,5-triazine, phosphonates and phosphonites,
e.g., dimethyl 2,5-
di-tert-buty1-4-hydroxybenzylphosphonate, acylaminophenols, e.g., 4-
hydroxylauranilide, esters
of 13-(3,5-ditert-buty1-4-hydroxyphenyl)propionic acid, e.g., pentaerythritol
tetrakis(3-(3,5-di-tert-
buty1-4-hydroxyphenyl)propionate), oc tadec y1-3 -(3 ,5-di-tert-b uty1-4-
hydroxyphenyl)propionate,
13-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid,
I-(3 ,5-dic yclohexy1-4-
hydroxyphenyppropionic acid, esters of 3,5-ditert-buty1-4-hydroxyphenylacetic
acid with mono-
or polyhydric alcohols. amides of f3-(3,5-ditert-butyl-4-
hydroxyphenyl)propionic acid, such as, for
example, N,N'-bis(3,5-ditert-buty1-4-hydroxyphenyl-
propionyl)hexamethylenediamine, vitamin E
(tocopherol) and derivatives. Mixtures of antioxidants may also be used.
[0052] The
antioxidants are typically used in amounts from 0.01 to 10 parts by weight,
preferably. from 0.1 to 5 parts by weight, and more preferably from 0.1 to 3
parts by weight, based
on 100 parts by weight of PVC.
XI. UV Absorbers and Light Stabilizers
[0053] Examples of UV absorbers and light stabilizers include 2-(2'-
hydroxyphenyl)benzotriazoles, such as 2-(2'-hydroxy-5'-methylpheny1)-
benzotriazole, 2-
hydroxybenzophenones, esters of unsubstituted or substituted benzoic acids,
such as 4-tert-
butylphenyl salicylate, phenyl salicylate, acrylates, nickel compounds,
oxalamides, such as 4,4'-
dioctyloxyoxanilide, 2,2'-
dioctyloxy-5,5'-ditert-butyloxanilide, 2-(2-hydroxypheny1)- 1,3,5-
triazines, such as 2,4,6-tris(2-hydroxy-4-octyloxypheny1)-1,3.5-triazine, 2-(2-
hydroxy-4-
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
14
octyloxypheny1)-4,6-bis(2,4-dimethylpheny1)-1,3,5-triazine, sterically
hindered amines, such as
bis(2,2.6,6-tetramethylpiperidin-4-y1) sebacate, bis(2.2,6,6-
tetramethylpiperidin-4-y1) succinate.
Mixtures of the UV absorbers and/or light stabilizers may also be used.
[0054] In another embodiment, the subject matter of the present disclosure
provides a process
for producing a PVC dry blend composition, the process comprising compounding
polyvinyl
chloride, a plasticizer, and a filler at temperatures of 25 to 70 C for a time
effective to form a dry
mixture having a bulk density greater than 0.5 g/cc. The plasticizer contains:
(i) dialkyl thiodiester
selected from dialkyl 3,3'-thiodipropionate, dialkyl 2,2'-thiodiacetate or
mixtures thereof, where
the alkyl groups are the same or different and are selected from C1-C18
linear, branched, cyclic or
aromatic groups; and (ii) epoxidized material selected from epoxidized oils,
epoxidized fatty acid
mono-esters, reaction mixtures prepared via trans-esterifying epoxidized oil
with alcohols, esters,
or mixtures thereof. In this process, the compounding step has a reduced
torque relative to the use
of the conventional plasticizers, such as phthalates, and an increased process
throughput relative
to the use of the conventional plasticizers, such as phthalates.
Halogenated polymers & Rubber
[0055] The plasticizer compositions of the invention may be added to
halogenated polymers,
such as PVC or rubber, by a compounding step. They are added in an amount
effective for
attaining plasticized compounds having reduced extraction, reduced volatility,
and increased
efficiency. Preferably, the plasticizer compositions are added to halogenated
polymers in the range
of from about 5 to about 200 parts, based on 100 parts halogen-containing
polymer or rubber.
More preferable is a range from about 10 to about 60 parts. These ranges
represent examples of
effective amounts. Other examples of effective amounts include: from about 2
to about 150 parts,
from about 5 to about 100 parts, from about 10 to about 60 parts, and from
about 20 to about 50
parts, based on 100 parts halogenated polymer or rubber.
[0056] Examples of halogen-containing polymers include polymers of vinyl
chloride, of
vinylidene chloride, vinyl resins whose structure contains vinyl chloride
units, such as copolymers
of vinyl chloride and alkylglycidyl acrylates, copolymers of vinyl chloride
and vinyl esters of
aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride
with esters of acrylic or
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
methacrylic acid and with acrylonitrile, copolymers of vinyl chloride with
diene compounds and
with unsaturated dicarboxylic acids or anhydrides of these, such as copolymers
of vinyl chloride
with diethyl maleate, diethyl fumarate or maleic anhydride. post chlorinated
polymers and
copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene
chloride with
unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde,
vinyl methyl ketone,
vinyl methyl ether, vinyl isobutyl ether and the like; polymers of yinylidene
chloride and
copolymers of the same with vinyl chloride and with other polymerizable
compounds; polymers
of vinyl chloroacetate and of dichlorodivinyl ether; chlorinated polymers of
vinyl acetate,
chlorinated polymeric esters of acrylic acid and of cc-substituted acrylic
acid; polymers of
chlorinated styrenes, such as dichlorostyrene; chlorinated rubbers;
chlorinated polymers of
ethylene; polymers and post chlorinated polymers of chlorobutadiene and
copolymers of these
with vinyl chloride, chlorinated natural or synthetic rubbers, and also
mixtures of the polymers
mentioned with themselves or with other polymerizable compounds. Preferably,
the halogenated
polymer is PVC, more preferably, a PVC homopolymer.
[0057] Rubbers that can be plasticized with the plasticizers of the current
disclosure include
styrene-butadiene rubber (SBR), acrylonitrile-butadiene- styrene (ABS),
polymethacrylate
butadiene styrene (MBS), Acrylonitrile-Butadiene Rubber (NBR), styrene-
acrylonitrile (SAN),
ethylene-vinyl acetate (EVA), chlorinated polyethylene (CPE), ethylene-
propylene diene
monomer (EPDM), acrylonitrile-butadiene (NBR), acrylonitrile-acrylate (MAR).
The rubbers can
be present alone or as mixtures with PVC or the graft polymers of PVC and EVA,
ABS or MBS.
Examples
[0058] The following examples further detail and explain the performance of
the inventive
compositions. Those skilled in the art will recognize many variations that arc
within the spirit of
the invention and scope of the claims.
Plasticizers
Di(2-ethylhexyl)-3.3'thiodipropionate (DOTDP) from TCI America.
Dimethy1-3,3'-thiodipropionate (DMTDP) from Galata Chemicals as Mark 5152.
Epoxidized soybean oil (ESO) from Galata Chemicals, LLC as Drapex 6.8.
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
16
Di(2-ethylhexyl)adipate (DOA), Di(isononyl)phthalate (DINP) and Di(2-
ethylhexyl)-tere-
phthalate (DOTP) from Aldrich.
[0059] Epoxidized 2-ethylhexyl soyate (EOS) was synthesized via
esterification of soy fatty
acids with 2-ethylhexanol followed by the epoxidation with hydrogen peroxide
in the presence of
formic acid.
[0060] The plasticizer blends were prepared by mixing the components for 1
hour at ambient
temperature to attain a homogeneous liquid.
Flexible Polyvinyl Chloride (PVC) Sample Preparation
[0061] The tested formulations included the following components: PVC resin
Oxy-450,
commercially available from Occidental Petroleum added at 100 parts;
plasticizers and their blends
added at 40 parts per 100 parts of PVC resin (phr); a liquid Ba/Zn stabilizer,
Mark 9502,
(marketed by Galata Chemicals LLC) and stearic acid lubricant were added to
all formulations at
2.5 and 0.2 phr, respectively
[0062] For the conversion of the powder form of the PVC formulations into a
usable form, a
sheet was prepared under standardized conditions using a two-roll mill (Dr.
Collin GmbH,
Ebersberg, Germany). The gap between the rolls was about 0.5 mm; the
temperature of the rolls
165 C; the time for preparation and homogenization: 5 minutes; and the sheet
thickness was 0.5
mm. The PVC sheet was continuously moved from the two sides to the center and
the enlargement
thus obtained was distributed over the gap with a wooden spatula over the roll
with intensive
homogenization of all components.
Testing of Plasticized Polyvinyl Chloride
Example 1: Shore A Hardness
[0063] Shore A Hardness of the formulations was determined in accordance with
ASTM
D2240, using a commercially available Durometer Type A hardness tester (Shore
Instrument &
Mfg Co, Jamaica, NY, USA). The tested samples were prepared in accordance with
the sample
preparation technique described above. Shore A Hardness results were measured
in triplicates.
Table 1 contains an average of the three readings. A lower number indicates a
softer material.
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
17
Table 1. Shore A Hardness of the selected plasticized compounds
Plasticizer Concentration of the Plasticizer Shore A
Hardness
Composition Plasticizer Components Loading, phr
(%)
DOTP/ESO ¨ control 93/7* 40 90
DINP/ESO ¨ control 93/7* 40 92
DOA/ESO ¨ control 93/7* 40 87
DOTDP/DOTP 50/50 40 87
DOTDP/DOA 50/50 40 85
DMTDP/ESO 93/7* 40 96
DMTDP/ESO 50/50 40 94
DOTDP 100 40 85
DOTDP/ESO 93/7* 40 85
DOTDP/ESO 50/50 40 87
DOTDP/EOS 75/25 40 87
DOTDP/EOS 50/50 28 90
DOTDP/ESO 93/7* 28 91
*In the examples, where ESO was added at 2-3 phr (or about 7% of the total
plasticizer composition), it served as a
secondary plasticizer typically present in plasticized compounds.
[0064] The data of Table 1 demonstrates that at an equal plasticizer
loading level of 40 phr: a)
both tested 3,3'-thiodipropionates (DMTDP and DOTDP) function as plasticizers,
resulting in soft
plasticized compounds; b) DMTDP and its blends, such as 50/50 DMTDP/ESO,
function as
general purpose type plasticizers similar to the DOTP and DINP controls (Shore
A Hardness of
96, 94, 90 and 92, respectively); c) DOTDP is unexpectedly found to be a
plasticizer of a very high
efficiency that is similar to but superior than the DOA control (Shore A
Hardness 85 and 87,
respectively); and d) DOTDP blends of this disclosure (DOTDP/DOTP, DOTDP/ESO,
DOTDP/EOS, and DOTDP/DOA) are also highly efficient plasticizers (Shore A
Hardness 87, 87,
87 and 85, respectively at 40 phr loadings).
[0065] The difference in the imparted Shore A Hardness of 90-92 that is
typical for general
purpose plasticizers, such as DINP and DOTP, and the Shore A Hardness of 85-87
imparted by
the high efficiency plasticizers, such as DOTDP and its blends with ESO and
EOS loaded at 40
phr, is significant, since it translates into a possibility of reducing
loadings of plasticizers of this
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
18
invention by about 30% (from 40 phr for DINP and DOTP to 28 phr for the 93/7
DOTDP/ESO
and 50/50 DOTDP/EOS plasticizer blends) in order to match Share A Hardness of
90-92 that was
imparted by the general purpose plasticizers (Table 1).
Example 2. Volatility
[0066] Volatility of the plasticized compounded milled sheets (thickness of
0.5 mm) was
calculated as a percent weight loss upon exposing the prepared PVC mill sheet
chips (25x25 mm)
to 100 C temperature over a 168 hour period of time. Weights were recorded
using an analytical
balance, and the results were measured in triplicates. Table 2 shows an
average of the three
readings.
Table 2. Weight loss (Volatility) of the selected plasticized compounds
Concentration Plasticizer Volatility (168
Plasticizer Composition of the Plasticizer Loading, phr hrs at 100 C), %
Components
(%)
DOTP/ES 0 ¨ control 93/7* 40 2.3
DINP/ESO ¨ control 93/7* 40 1.6
DOA/ESO ¨ control 93/7* 40 8.5
DMTDP/ESBO 93/7* 40 4.4
DOTDP/ESO 93/7* 40 2.9
DOTDP/ESO 50/50 40 2.3
DOTDP/EOS 25/75 40 1.9
DOTDP/EOS 50/50 40 1.9
In the examples, where ESO was added at 2-3 phr (or about 7% of the total
plasticizer composition), it served as a
secondary plasticizer typically present in plasticized compounds.
[0067] The results of Table 2 demonstrate that compounds plasticized by both
DMTDP and
DOTDP are less volatile than those plasticized with DOA (weight loss 4.4, 2.9,
and 8.5%,
respectively). Commonly, high efficiency plasticizes impart high volatility on
the plasticized
compounds, while general purpose plasticizers of the standard efficiency
impart lower volatility
on the plasticized compounds. Unexpectedly, a 50/50 DOTDP/ESO high efficiency
blend loaded
at 40 phr was found to have the same volatility as DOTP at 40 phr, a general
purpose plasticizer
(weight loss of 2.3% for both), and the 25/75 and 50/50 DOTDP/EOS high
efficiency blend loaded
at 40 phr resulted in a less volatile compound than the DOTP control (weight
loss of 1.9, 1.9 and
2.3%, respectively). Therefore, Example 2 (Table 2) demonstrates that
plasticizers of the present
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
19
subject matter are not only highly efficient, but result in a relatively low
volatility in the plasticized
compounds.
Example 3. Flexibility of compounds at low temperatures
[0068] The brittleness temperature was measured in accordance with ASTM D 746,
using a
Tinius Olsen Brittleness Tester. A specimen was prepared via milling the
compound as described
in the Flexible Polyvinyl Chloride (PVC) Sample Preparation section above,
compression-
molding it into a plaque with the use of a Wabash press, and then cutting it
using a cutting die of
2.5 in x 0.25 in x 0.075 in. The temperature was controlled using a dry
ice/acetone bath. Results
of the test are listed in Table 3.
Table 3. Low Temperature Brittleness Point of the selected plasticized
compounds
Plasticizer Concentration of the Plasticizer Low Temperature
Composition Plasticizer Components Loading, Brittleness Point,
(%) phr C
DINP/ESO 93/7* 40 -23
control
DOA/ESO ¨ control 93/7* 40 -38
911P ¨ control 100 40 -28
DOTDP/ES 0 93/7* 40 -34
DOTDP/ES 0 50/50 40 -23
DOTDP/EOS 25/75 40 -30
DOTDP/EOS 50/50 40 -30
DOTDP/EOS 75/25 40 -35
*In the examples, where ESO was added at 2-3 phr (or about 7% of the total
plasticizer composition), it served as a
secondary plasticizer typically present in plasticized compounds.
[0069] The results of Table 3 demonstrate that DOTDP and its 75/25 blend with
EOS,
plasticizers of the present subject matter, impart low temperature flexibility
comparable to that of
DOA (low temperature brittleness point -34, -35 and -38 C, respectively). A
50/50 DOTDP/ESO
blend imparted low temperature flexibility similar to that of general purpose
branched phthalate
plasticizers, such as DINP (low temperature brittleness point of -23 C). The
25/75 and 50/50
blends of DOTDP with EOS imparted low temperature flexibility similar to that
of linear phthalate
plasticizers, such as 911P (low temperature brittleness points of -30, -30 and
-28 C, respectively.
Example 3 thus demonstrates high effectiveness of DOTDP and its blends to
maintain flexibility
of the plasticized compounds at low temperatures.
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
Example 4. Extraction Resistance
[0070] Extraction of the plasticizers from the flexible PVC milled sheets
(thickness of 0.5 mm)
was measured by submersing weighted samples of known surface area in: a)
sunflower oil at 60 C
for 24 hours, and b) hexane at ambient temperature for 24 hours. The weight
loss associated with
extraction of the plasticizers was calculated in mg/dm2 upon removal of the
samples from hexane
or the oil; and in the case of oil, wiping off any excess oil, rinsing the
samples with isopropanol to
completely remove the oil from the surface and air drying the samples. Weights
were recorded
using an analytical balance. The results were measured in triplicate. Results
in Table 4 are an
average of the three readings.
Table 4. Extractability of the selected plasticized compounds
Plasticizer Concentration of the Plasticizer Extraction in Extraction
Composition Plasticizer Components Loading, phr Hexane, in
(%) mg/dm2 Sunflower
oil, mg/dm2
DOTP/ES 0 93/7* 40 338 187
control
DOA/ES 0 93/7* 40 391 366
control
DOTDP/ES 0 93/7* 40 255 326
DOTDP/ES 0 93/7* 28 54 148
DOTDP/ES 0 50/50 40 213 290
DOTDP/EOS 50/50 28 90 138
*In the examples, where ESO was added at 2-3 phr (or about 7% of the total
plasticizer composition), it served as a
secondary plasticizer typically present in plasticized compounds.
[0071] The data of Table 4 illustrates the results of extracting compounds
plasticized with the
plasticizers of the present disclosure and the DOTP and DOA controls.
Extraction from
compounds plasticized with DOTDP and the 50/50 DOTDP/ESO blend loaded at 40
phr was lower
than that of DOA in both hexane (255 and 213 vs. 391 mg/dm2, respectively) and
sunflower oil
(326 and 290 vs. 366 mg/dm2, respectively). Loaded at 28 phr to attain similar
Shore A Hardness,
extraction of compounds plasticized with DOTDP was lower than that of DOTP
loaded at 40 phr
in both hexane (54 vs. 338 mg/dm2, respectively) and sunflower oil (148 vs.
187 mg/dm2,
respectively). Similarly, loaded at 28 phr to attain comparable Shore A
Hardness, extraction of
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
21
compounds plasticized with the 50/50 DOTDP/EOS blend was also lower than that
of DOTP
loaded at 40 phr in both hexane (90 vs. 338 mg/dm2, respectively) and
sunflower oil (138 vs. 187
mg/dm2, respectively).
[0072] The results of Table 4 demonstrate that compounds plasticized with
the plasticizers of
the present subject matter exhibit lower extraction values, and consequently
are less extractable
and of higher extraction resistance in both non-polar (hexane) and polar
(sunflower oil) organic
liquids.
Example 5. Volume Resistivity
[0073] Volume resistivity of the plasticized compounds was measured in
accordance with
ASTM D 257-91. The compound also contained calcium carbonate, a filler at 20
phr. The results
are expressed in Ohm. meters in Table 5.
Table 5. Volume Resistivity of the selected plasticized compounds
Plasticizer Concentration of the Plasticizer Loading, Volume Resistivity
Composition Plasticizer Components phr (Slim)
(%)
DOA/ESO 93/7* 40 2.28E+11
control
DOTDP/ES 0 93/7* 40 1.48E+12
DOTDP/ES 0 50/50 40 8.77E+12
*In the examples, where ESO was added at 2-3 phr (or about 7% of the total
plasticizer composition), it served as a
secondary plasticizer typically present in plasticized compounds.
[0074] The experimental data of Table 5 illustrate that the Volume
Resistivity imparted by
DOTDP and its 50/50 blend with ESO was substantially greater than that of the
DOA control,
demonstrating that the plasticizers of this invention are suitable for use in
wire and cable
applications, requiring high volume resistivity characteristics.
Example 6. Heat Stability
[0075] Heat stability of the plasticized compounds was measured using the
following
procedure. The milled sheets were prepared as described in the Sample
Preparation Section. The
15 mm wide strips were cut from each milled sheet such that eight rectangular
samples (15 mm x
CA 02987581 2017-11-28
WO 2017/011065 PCT/US2016/031704
22
mm) from each sheet were produced. The samples were placed in an oven (Blue M
Company,
New Columbia, PA, USA) operating at 190 C for thermal aging. The samples were
removed from
the oven at the rate of one sample every ten minutes during a two-hour period.
Assessment of the
thermal stability of the flexible PVC formulations was carried out by
determining the discoloration
due to the polymer degradation. The Yellowness Index (ASTM D 1925-70
Yellowness Index of
plastics) was measured and recorded for each sample using the microprocessor
Hunterlab Labscan
Spectro Colorimeter, Type 5100. The heat stability data shown in Table 6 are
expressed in the
decomposition time representing the complete darkening of the specimen as a
result of the thermal
decomposition. The longer the decomposition time the more heat-stable compound
is.
Table 6. Decomposition Time of the selected plasticized compounds
Plasticizer Concentration of the
Plasticizer Decomposition
Composition Plasticizer Components Loading, phr Time, min.
(%)
DOTP/ES 0 ¨ control 93/7* 40 75
DINP/ESO ¨ control 93/7* 40 75
DOA/ESO ¨ control 93/7* 40 60
DOTDP/ES 0 75/25 40 70
DOTDP/ES 0 50/50 40 >120
DOTDP/EOS 75/25 40 90
DOTDP/EOS 50/50 40 >120
DOTDP/D0A/ESO 43/50/7 40 75
In the examples, where ESO was added at 2-3 phi (or about 7% of the total
plasticizer composition), it served as a
secondary plasticizer typically present in plasticized compounds.
[0076] The results in Table 6 demonstrate that compounding of DOTDP and the
DOTDP/ESO
and DOTDP/EOS blends of this disclosure with PVC resin increases the
Decomposition Time of
the plasticized compounds to 90 ¨ 120+ min. over the compounds containing the
control
plasticizers, which demonstrate decomposition times of 60-75 min.
Interestingly, combining
DOTDP with DOA also surprisingly resulted in the increased Decomposition Time
of 75 min.
compared with 60 min., imparted by the DOA control. Consequently, DOTDP and
its blends with
epoxidized oils and/or epoxidized mono-esters of fatty acids impart the
increased heat stability of
the plasticized compounds.
